Glazing perimeter anticondensation coating technology

ABSTRACT

The invention provides a glass pane that has a transparent electrically conductive coating on a surface of the glass pane, such that the glass pane has a coated surface. The coated surface has a central region and a perimeter region. The transparent electrically conductive coating has a higher electrical conductivity at the central region than it does at the perimeter region. In some embodiments, the coated glass pane is part of an IG unit. Also provided are methods of producing a coated glass pane having an anti-condensation perimeter region.

FIELD OF THE INVENTION

The present invention relates generally to thin film coatings for glassand other substrates. More particularly, this invention relates toheat-treated transparent electrically conductive coatings.

BACKGROUND OF THE INVENTION

Water sometimes collects on windows and other glazing assemblies, likeany other surfaces, in the form of condensation. Condensation forms, forexample, when a window surface is cooled to the point where the rate ofevaporation from the surface is lower than the rate of condensation tothe surface from the air. A cooler surface or a higher moisture contentin the air will make condensation more likely. Consider a winterenvironment where the outdoor conditions are relatively cold and theindoor environment is relatively warm, and at least somewhat humid. Whencondensation forms on a glazing in such environments, it is typicallymore likely to occur at the perimeter of the room-side glass surface,i.e., near the frame. This is because the edge region of a multiple-paneinsulating glass unit (“IG unit”) typically is less thermally insulativethan its center region. As will be appreciated, the center region of anIG unit has at least one thermally insulative between-pane spaceseparating two glass panes. This space may contain air, a mix of air andthermally insulative gas (e.g., argon), or a vacuum. As a result, heattransfer through the center region of an IG unit is particularly low.While heat transfer at the edge region of an IG unit may also be low, itis typically somewhat higher than at the central region due to thepresence of a spacer and sealant connecting the panes. The spacer andsealant, while engineered to reduce heat transfer, provide a thermalconduction pathway that is not present at the center region of an IGunit.

Thus, in winter environments, the perimeter of the room-side glasssurface of an IG unit will typically be cooler than the center and ismore likely to form condensation than is the center region. Whileparticular winter conditions have been mentioned, it will be appreciatedthat the perimeter regions of a glazing can form condensation in variousseasons, climates, environments, and glazing arrangements. Thus, itwould be desirable to provide a coating system that reduces thepotential for glazing perimeter condensation to occur.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic front view of a coated glass pane in accordancewith certain embodiments of the present invention;

FIG. 2 is a schematic front view of the coated glass pane of FIG. 1mounted to a frame in accordance with certain embodiments of theinvention;

FIG. 3 is a schematic, broken-away, cross-sectional side view of amultiple-pane insulating glass unit mounted to a frame in accordancewith certain embodiments of the invention;

FIG. 4 is a broken-away schematic cross-sectional view of a glass panebearing a transparent electrically conductive coating in accordance withcertain embodiments of the invention;

FIG. 5 is a broken-away schematic cross-sectional view of a glass panebearing a transparent electrically conductive coating in accordance withother embodiments of the invention;

FIG. 6 is a broken-away schematic cross-sectional view of a glass panebearing a transparent electrically conductive coating and atitanium-oxide containing film in accordance with still otherembodiments of the invention;

FIG. 7 is a broken-away schematic side view of a production line inaccordance with certain embodiments of the present invention; and

FIG. 8 is a schematic top view of one of the heat treatment devices ofFIG. 7.

SUMMARY OF THE INVENTION

In some embodiments, the invention provides a glass pane having atransparent electrically conductive coating on a surface of the glasspane, such that the glass pane has a coated surface. The coated surfacehas a central region and a perimeter region. The transparentelectrically conductive coating has a higher electrical conductivity atthe central region than it does at the perimeter region.

Certain embodiments of the invention provide a multiple-pane insulatingglass unit that includes at least two glass panes and has at least onebetween-pane space. The multiple pane insulating glass unit has twoexternal surfaces and a plurality of internal surfaces. Each of theinternal surfaces is exposed to a between-pane space of themultiple-pane insulating glass unit. Each of the two external surfacesis exposed to an environment external to the multiple-pane insulatingglass unit. A desired one of the two external surfaces has a transparentelectrically conductive coating, so as to define a coated surface. Thecoated surface has a central region and a perimeter region. Thetransparent electrically conductive coating has a higher electricalconductivity at the central region than it does at the perimeter region.

Some embodiments of the invention provide a glazing that includes aframe and a multiple-pane insulating glass unit. The multiple-paneinsulating glass unit is mounted to the frame. The multiple-paneinsulating glass unit includes an inboard glass pane and an outboardglass pane and has at least one between-pane space. The outboard glasspane defines an external surface that is exposed to periodic contactwith rain. The inboard glass pane defines an external surface that isexposed to a room-side environment inside a building. The externalsurface of the inboard glass pane has a transparent electricallyconductive coating, so as to define a coated surface. The coated surfacehas a central region and a perimeter region. The transparentelectrically conductive coating has a higher electrical conductivity atthe central region than it does at the perimeter region.

In certain embodiments, the invention provides a heat treatment method.The method involves providing a glass pane having a transparentelectrically conductive coating on a surface of the glass pane, suchthat the glass pane has a coated surface. The coated surface has acentral region and a perimeter region. The method includes selectivelyheat treating either the central region or the perimeter region of thecoated surface such that the transparent electrically conductive coatinghas a higher electrical conductivity at the central region than it doesat the perimeter region.

In some embodiments, the invention provides a glass pane having atransparent electrically conductive coating on a surface of the glasspane, such that the glass pane has a coated surface. In the presentembodiments, the glass pane is tempered glass having a surface stress ofgreater than 10,000 psi. The coated surface has a central region and aperimeter region. The transparent electrically conductive coating has ahigher electrical conductivity at the central region than it does at theperimeter region. Preferably, the transparent electrically conductivecoating includes a transparent electrically conductive oxide film thatis oxidized to a different extent at the central region than it is atthe perimeter region. In preferred embodiments, the transparentelectrically conductive coating has a sheet resistance that is at least5 Ω/square higher at the perimeter region than it is at the centralregion. Preferably, the transparent electrically conductive coating hasa visible transmission that is substantially the same at the perimeterregion as it is at the central region. For example, the visibletransmission at the perimeter region may be no more than 2% differentfrom the visible transmission at the central region. In preferredembodiments, the transparent electrically conductive coating has athickness of less than 3,000 Å, and at the central region, thetransparent electrically conductive coating has a sheet resistance ofless than 30 Ω/square in combination with the coated glass pane having amonolithic visible transmittance of greater than 0.82.

Some embodiments of the invention provide a heat treatment method. Themethod includes providing a glass pane having a transparent electricallyconductive coating on a surface of the glass pane, such that the glasspane has a coated surface. The coated surface has a central region and aperimeter region. In the present embodiments, the method involvesperforming first and second heat treatments. The first heat treatmentinvolves tempering the coated glass pane. The second heat treatmentinvolves selectively heat treating either the central region or theperimeter region of the coated surface, such that the transparentelectrically conductive coating has a higher electrical conductivity atthe central region than it does at the perimeter region.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The following detailed description is to be read with reference to thedrawings, in which like elements in different drawings have likereference numerals. The drawings, which are not necessarily to scale,depict selected embodiments and are not intended to limit the scope ofthe invention. Skilled artisans will recognize that the examplesprovided herein have many useful alternatives that fall within the scopeof the invention.

The invention provides a coated glass pane having an anti-condensationperimeter region. The glass pane 10′ has a transparent electricallyconductive coating 107 on a surface 18 of the glass pane, such that theglass pane has a coated surface. The term “transparent” here means thecoating has a visible transmission of at least 20%. The coated surface18 has a central region 205 and a perimeter region 210. The coating 107has higher electrical conductivity at the central region 205 than itdoes at the perimeter region 210.

Preferably, the electrical conductivity of the coating 107 as averagedover the entire central region 205 is higher than the electricalconductivity of the coating 107 as averaged over the entire perimeterregion 210. In some cases, the electrical conductivity of the coating107 is higher at all areas of the central region 205 than it is at allareas of the perimeter region 210.

By providing the perimeter region 210 with lower conductivity than thecentral region 205, condensation will be less likely to occur at theperimeter region under certain conditions. Consider the performance ofthe IG unit 110 of FIG. 3 in winter conditions like those discussedabove. The perimeter region 210 of the room-side surface 18 is adjacentto the spacer and sealant at the edge of the IG unit. As a result, theperimeter region will lose more heat due to the adjacent outward flow ofheat by conduction through the panes, spacer, and sealant. The presentinvention seeks to compensate for this phenomenon by providing theperimeter region 210 with lower conductivity than the central region205. For transparent electrically conductive coatings, lowerconductivity (i.e., higher resistivity) correlates with higheremissivity. Higher emissivity means the surface will more easily absorb(as opposed to reflect) radiation. This causes the coating 107 at theperimeter region 210 to be less effective as a heat shield. Theperimeter region 210 of the coated surface 18 is therefore warmed byradiative heat transfer from the interior environment. This keeps theperimeter region 210 warmer than it would be otherwise, thereby reducingthe likelihood of condensation forming on the perimeter region

The desired arrangement of different electrical conductivity levels canbe created by a process that includes selectively heat treating thecentral region 205 or the perimeter region 210. For example, the centralregion 205 of the coated surface 18 can be heat treated by a differentprocess than is the perimeter region. Alternatively, heat treatment canbe performed only on the central region. More will be said of thislater.

FIG. 1 shows a glass pane 10′ having a surface 18 coated with atransparent electrically conductive (“TC”) coating 107. The TC coating107 can be any transparent electrically conductive coating. Insofar asthe glass pane 10′ is concerned, a variety of well-known glass types canbe used, such as soda-lime glass. In some cases, it may be desirable touse “white glass,” a low iron glass, etc. In some embodiments, the glasspane is part of a window, door, skylight, or other glazing. For certainapplications, it may be desirable that the glass pane be tinted glass.

Glass panes of various sizes can be used in the present invention.Commonly, large-area glass panes are used. Certain embodiments involve aglass pane having a major dimension (e.g., a length or width) of atleast 0.075 meter (e.g., between 0.075 meter and 4 meters), such as atleast 0.1 meter, or in some cases at least 0.5 meter, at least 1 meter,or at least 1.5 meters (e.g., between 2 and 4 meters). The smaller panesizes may be used, for example, in a true divided lite glazing.

Glass panes of various thicknesses can be used in the present invention.In some embodiments, the glass pane has a thickness of 1-14 mm, such as2-14 mm. Certain embodiments involve a substrate with a thickness ofbetween about 2.3 mm and about 4.8 mm, and perhaps more preferablybetween about 2.5 mm and about 4.8 mm. In one particular embodiment, asheet of soda-lime glass with a thickness of about 3 mm is used.

The glass pane 10′ has opposed surfaces (16 and 18), which preferablyare major surfaces (as opposed to edge surfaces). In some cases, surface16 is destined to be an internal surface exposed to a between-pane spaceof a multiple-pane insulating glazing unit (“IG unit”), while surface 18is destined to be an external surface exposed to an interior of abuilding. This, however, is not the case in all embodiments.

Preferably, the TC coating 107 includes a transparent conductive oxidefilm 20. For example, the TC coating 107 can optionally be an indium tinoxide based coating. Thus, in some cases, the TC coating 107 includes atransparent conductive oxide film comprising indium tin oxide. In suchcases, the indium tin oxide film comprises indium tin oxide, optionallytogether with one or more other materials. If desired, zinc, aluminum,antimony, fluorine, carbon nanotubes, or other components can beincluded in the film. When provided, the indium tin oxide filmpreferably consists essentially of (e.g., contains more than 95% byweight), or consists of, indium tin oxide. A suitable indium tin oxidefilm can contain various relative percentages of indium and tin. On ametal-only basis, indium preferably is the major constituent. That is,indium preferably accounts for more than 50% of the film's total metalweight. The composition of such a film, on a metal-only basis, canoptionally range from about 75% indium/25% tin to about 95% indium/5%tin, such as about 90% indium/10% tin.

The TC coating 107 can alternatively include a transparent conductiveoxide film comprising fluorinated tin oxide (“FTO”), doped zinc oxide,such as aluminum-doped zinc oxide (“AZO”), doped titanium dioxide, suchas niobium-doped TiO₂ (“NTO”), or any other transparent conductive oxidematerial.

In some cases, the TC coating 107 comprises a transparent conductiveoxide film 20 having a thickness of less than 3,000 Å, less than 2,000Å, less than 1,800 Å, or even less than 1,500 Å, such as from 1,050 Å to1,450 Å. The TC coating 107 of any embodiment of the present disclosurecan optionally include a TCO film 20 having a thickness in any one ormore of these ranges. All thicknesses reported herein are physicalthicknesses, unless otherwise specified.

In preferred embodiments, the TC coating 107 includes a transparentelectrically conductive oxide (“TCO”) film 20 that is oxidized to adifferent extent at the perimeter region 210 than it is at the centralregion 205. Preferably, the extent to which the TCO film 20 is oxidizedas averaged over the entire central region 205 is different than theextent to which the TCO film is oxidized as averaged over the entireperimeter region 210. In some cases, the TCO film 20 is oxidized to adifferent extent (i.e., to a greater extent, or to a lesser extent) atall areas of the perimeter region 210 than it is at all areas of thecentral region 205.

The transparent conductive oxide film 20 can optionally be underoxidized at the perimeter region 210, such that the film at theperimeter region has a lower electrical conductivity than at the centralregion 205. Alternatively, the transparent conductive oxide film 20 canbe over oxidized at the perimeter region 210, such the film at theperimeter region has a lower electrical conductivity than at the centralregion 205. In some embodiments, the TC coating 107 includes an indiumtin oxide film that is oxidized to a different extent at the perimeterregion than it is at the central region.

The TC coating 107 has a sheet resistance that is higher at theperimeter region 210 than it is at the central region 205. Preferably,the sheet resistance is at least 5 Ω/square higher at the perimeterregion 210 than it is at the central region 205. In some cases, thesheet resistance is at least 7.5 Ω/square, or at least 10 Ω/square,higher at the perimeter region 210 than it is at the central region 205.Sheet resistance can be measured in standard fashion using a non-contactsheet resistance meter.

Preferably, the sheet resistance of the coating 107 as averaged over theentire perimeter region 210 is higher than the sheet resistance of thecoating 107 as averaged over the entire central region 205. In suchcases, the average sheet resistance at the perimeter region 210 may behigher than the average sheet resistance at the central region 205 byone or more of the differentials noted in the previous paragraph. Incertain embodiments, the sheet resistance of the coating 107 is higherat all areas of the perimeter region 210 than it is at all areas of thecentral region 205.

The visible transmission of the coating 107 is substantially the same(i.e., having a difference in T_(vis) of less than 10%) at the perimeterregion 210 as it is at the central region 205. Preferably, the visibletransmission at the perimeter region 210 is different from the visibletransmission at the central region 205 by no more than 5%, no more than3%, or no more than 2%, or no more than 1%.

The term “visible transmission” is well known in the art and is usedherein in accordance with its well-known meaning to refer to thepercentage of all incident visible radiation that is transmitted througha pane or IG unit. Visible radiation constitutes the wavelength range ofbetween about 380 nm and about 780 nm. Visible transmittance, as well asvisible reflectance, can be determined in accordance with NFRC 300-2014,Standard Test Method for Determining the Solar and Infrared OpticalProperties of Glazing Materials and Fading Resistance of Systems. Thewell-known WINDOW 7.1 computer program can be used in calculating theseand other reported optical properties.

The thickness of the coating 107 is at least substantially the same(i.e., with any difference being less than 10%) at the perimeter region210 as it is at the central region 205. The thickness of the coating 107at the perimeter region 210 preferably is different from the thicknessat the central region 205 by no more than 5%, no more than 3%, or nomore than 2%. It may well be the case that there is no measurablethickness difference between these two regions.

As noted above, the desired arrangement of different electricalconductivity levels can be created by a production process that includesselectively heat treating the central region 205 or the perimeter region210. The overall production process employs one or more heat treatmenttechniques. Preferably, the production process includes at least oneselective heat treatment technique performed such that the rear surface16 of the glass pane 10′ is maintained at a temperature of 150 degreesC. or less during the selective heat treatment. This temperature can bemeasured, for example, using pyrometry.

To limit heating of the glass during the selective heat treatment, theselective heat treatment technique preferably provides an irradiance atthe TC coating 107 of 15 kW/cm² or greater, e.g., in the range of 15-45kW/cm², or even 20 kW/cm² or greater, e.g., in the range of 20-45kW/cm². In some cases, the irradiance is greater than 30 kW/cm², e.g.,in the range of 30-45 kW/cm². By using such high energy density, theheat desired for converting the TC coating 107 is delivered rapidly(e.g., in less than 1 second, less than ½ second, or less than 50milliseconds). This beneficially limits the heating of the glass.

In certain embodiments of this nature, since the glass pane 10′ ismaintained at a relatively low temperature during the selective heattreatment, the pane 10′ is annealed glass prior to and after theselective heat treatment. For example, in some cases, the glass pane 10′is annealed glass having a surface stress, prior to and after theselective heat treatment, of less than 3,500 psi, less than 3,000 psi,or less than 2,500 psi. Surface stress can be determined using a grazingangle surface polarimeter as specified in ASTM C1048 and ASTM C1279, theteachings of which are incorporated herein by reference.

In FIGS. 1 and 2, the perimeter region 210 of the coated surface 18surrounds the central region 205. Both of these regions 205, 210 arecoated (in some cases, the entirety of both regions are coated) with thetransparent electrically conductive coating 107, yet the coating at thecentral region is more electrically conductive than the coating at theperimeter region. Preferably, the perimeter region 210 entirelysurrounds (i.e., surrounds on all sides) the central region 205. Thewidth W of the perimeter region 210 can be varied. Generally, it will beless than 8 inches and greater than ⅛ inch. In preferred embodiments,the width W is 6 inches or less, while being greater than ¼ inch, suchas greater than ½ inch but less than 4 inches, or greater than ½ inchbut less than 3 inches. In FIGS. 1 and 2, the width W of the perimeterregion 210 is the same all the way around the perimeter of the coatedsurface 18. This, however, is not required. For example, the width W ofthe perimeter region 210 may be greater on the top and bottom sides (asseen in FIG. 1) than it is on the left and right sides. In manyembodiments, however, the width W of the perimeter region 210 will be atleast substantially the same (i.e., varying by no more than 10%) all wayaround the perimeter of the coated surface 18.

The perimeter region 210 preferably constitutes less than 50% of theentire surface area of the coated surface 18. While the size anddimensions of the coated surface 18 and its perimeter region 210 will bevaried to accommodate different glazing situations, it may be preferredthat the perimeter region 210 constitute less than 45%, or even lessthan 40% of the area of the coated surface 18. A preferred range may befrom 0.05 to 0.4, such as from 0.1 to 0.4, or from 0.2 to 0.4. As justone non-limiting example, when the pane surface 18 has dimensions of 36inches by 44 inches, and when the width W of the perimeter region 210 isfour inches, the ratio in question is 0.36.

In some cases, unlike the embodiment shown in FIG. 1, the perimeterregion 210 having the higher sheet resistance does not extend all theway to the edge of the glass pane 10′. Since the outermost edge regionof the glass pane 10′ will typically be enclosed by a shoulder 350 of aframe 300 (as shown in FIG. 3), the higher sheet resistance perimeterregion 210 may actually be spaced inwardly from the edge of the glasspane. Thus, when the perimeter region 210 is heat treated selectively,this can optionally involve controlling the selective heat treatment soit does not treat the very outermost edge region of the coated surface18, but rather only flash treats a perimeter region that is spacedinwardly of the edge of the coated surface. Accordingly, while theperimeter region of the coated surface will in some embodiments beadjacent to the frame and surrounding the central region of the coatedsurface, the perimeter region may actually be located inwardly of theframe (i.e., closer to the central region of the coated surface).

The transparent electrically conductive coating 107 will typicallyextend all the way to the edge of the glass pane 10′, as shown in FIGS.1 and 3. If desired, however, edge deletion can be performed so as toremove an area of the coating 107 that is destined to be enclosed by ashoulder 350 of a frame 300. In such cases, the perimeter region 210(which bears the TC coating 107) will be located inwardly of the edgedeleted area, and the central region 205 will be located inwardly of theperimeter region 210.

In FIGS. 1 and 2, the dashed line schematically depicts a discreteinterface between the perimeter region 210 and the central region 205.Depending on the technique used for the selective heat treatment,however, there may not be a discrete transition line between these tworegions. For example, some embodiments provide a gradual transitionbetween the higher conductivity central region 205 and the lowerconductivity perimeter region 210. This may be the case, for example,when a flash bulb device is moved about the perimeter of the coatedsurface 18 so as to selectively flash treat the perimeter region 210. Insuch cases, the radiation from the flash bulb device may reach thecoating 107 at a level that decreases gradually with increasing distancefrom the flash bulb device. Thus, in moving inwardly from the perimeterregion 210 to the central region 205, there may be a gradient in termsof the film's oxidation level and electrical conductivity. In othercases (when a mask is used, when certain laser treatments are used,etc.), the transition between these two regions will be more discrete.

In some embodiments, the glass pane 10′ is tempered glass. The temperedglass preferably has a surface stress of greater than 10,000 psi, suchas greater than 10,000 psi and less than 15,000 psi, or perhapsoptimally between 12,000 psi and 15,000 psi. As noted above, the glasspane 10′ has a transparent electrically conductive coating 107 on asurface 18 of the glass pane, such that the glass pane has a coatedsurface. In the present embodiments, the coating 107 is subjected to thetempering temperatures together with the glass pane 10′. The coatedsurface 18 has a central region 205 and a perimeter region 210. Thetransparent electrically conductive coating 107 has a higher electricalconductivity at the central region 205 than it does at the perimeterregion 210. As noted above, the transparent electrically conductivecoating 107 preferably includes a transparent electrically conductiveoxide film 20 (which may comprise, consist essentially, or consist ofITO) that is oxidized to a different extent at the central region 205than it is at the perimeter region 210. In preferred embodiments, thetransparent electrically conductive coating 107 has a sheet resistancethat is at least 5 Ω/square higher at the perimeter region 210 than itis at the central region 205. Any of the sheet resistance differentialsdescribed above can be provided in the present tempered coated glassembodiments. Further, as detailed above, the transparent electricallyconductive coating 107 has a visible transmission that is substantiallythe same at the perimeter region 210 as it is at the central region 205.The visible transmission at the perimeter region 210 may be, forexample, no more than 5% (or no more than 3%, or no more than 2%, or nomore than 1%) different from the visible transmission at the centralregion 205. In preferred embodiments, the transparent electricallyconductive coating 107 has a thickness of less than 3,000 Å, and at thecentral region 205, the transparent electrically conductive coating hasa sheet resistance of less than 30 Ω/square in combination with thecoated glass pane 10′ having a monolithic visible transmittance ofgreater than 0.82. Any of the ranges described above for thicknesses,sheet resistance, and visible transmission can be provided in thepresent tempered coated glass embodiments. Moreover, any of the filmmaterials/compositions and layer stack arrangements described above canbe provided in the present embodiments. Non-limiting methods forproducing such tempered coated glass are described later.

In connection with the transparent electrically conductive coating 107,FIGS. 4 and 5 depict two exemplary embodiments wherein the coating 107includes a transparent conductive oxide film 20 and an optional overcoatfilm 100. In the embodiment of FIG. 4, the coating 107 includes, fromsurface 18 outwardly, the transparent conductive oxide film 20 and theoptional overcoat film 100. If desired, a base film 15 can be added. Forexample, in the embodiment of FIG. 5, the coating 107 includes, fromsurface 18 outwardly, an optional base film 15, the transparentconductive oxide film 20, and the optional overcoat film 100. Films 15,20, and 100 can be provided in the form of discrete layers, thicknessesof graded film, or a combination of both including at least one discretelayer and at least one thickness of graded film. While the base film 15is shown as a single layer, it can alternatively be a plurality oflayers.

When provided, the overcoat film 100 is located over the transparentconductive oxide film 20. In some cases, the overcoat film 100 comprisessilicon nitride. Alternatively, the overcoat film 100 can comprisesilicon oxynitride or silicon dioxide. In still other cases, theovercoat film 100 comprises tin oxide. In such cases, the tinoxide-containing overcoat film is devoid of indium oxide. In certainembodiments, the overcoat film 100 contains at least 75% tin, at least85% tin, or at least 95% tin (on a metal-only basis), while also beingdevoid of indium oxide. For example, the overcoat film 100 may consistof (or at least consist essentially of) tin oxide (e.g., SnO₂).

The coating 107 can optionally include a nitride film between thetransparent conductive oxide film 20 and the overcoat film 100. Whenprovided, the nitride film may comprise one or more of silicon nitride,aluminum nitride, and titanium nitride. For example, a thin film ofsilicon nitride can optionally be positioned directly between (i.e., soas to contact both) the transparent conductive oxide film 20 and anovercoat film 100 comprising silicon oxynitride. When provided, thissilicon nitride film may have a thickness of less than 250 Å, or evenless than 200 Å, e.g., about 150 Å.

In other embodiments, the overcoat film 100 is in contact with thetransparent conductive oxide film 20. Providing the overcoat film 100directly over (i.e., so as to be in contact with) the underlyingtransparent conductive oxide film 20 can be advantageous. For example,providing fewer layers and interfaces may be desirable in connectionwith optical properties, stress, or both. Moreover, material, energy,and cost can be conserved by providing fewer layers.

When provided, the optional base film 15 has a thickness of 50 Å ormore, such as about 70-300 Å. In certain embodiments, the coating 107includes a base film comprising silicon dioxide (optionally togetherwith some alumina), titanium dioxide, alumina, or tin oxide at athickness of 75-150 Å. In one non-limiting example, the coating 107consists of the following layers (in the following sequence movingoutwardly from surface 18 of the glass pane 10′): silicon dioxide (100Å)/ITO (1,350 Å)/Si_(x)O_(y)N_(z) (940 Å).

The invention also provides embodiments wherein the transparentconductive oxide film 20 is directly on (i.e., in contact with) thesubstrate surface 18. In one non-limiting example, the coating 107consists of the following layers (in the following sequence movingoutwardly from surface 18 of the glass pane 10′): ITO (1,325 Å)/Si₃N₄(440 Å).

The coating 107 can optionally further include an oxynitride filmlocated on the overcoat film 100. When provided, this oxynitride filmcan have a thickness of between 100 Å and 1,300 Å, such as between 400 Åand 900 Å. The oxynitride film can optionally be directly over (i.e., soas to contact) the overcoat film 100. The oxynitride film may comprisealuminum, oxygen, and nitrogen. In some cases, the oxynitride film is anexposed outermost film of the coating 107. In one non-limiting example,the coating 107 consists of the following layers (in the followingsequence moving outwardly from surface 18 of the glass pane 10′):silicon dioxide (100 Å)/ITO (1,400 Å)/Si_(x)O_(y)N_(z) (940 Å).

Some embodiments of the invention provide a film comprising titaniumoxide 70 over the transparent electrically conductive coating 107.Reference is made to FIG. 6. When provided, the film comprising titaniumoxide 70 preferably is an exposed, outermost film. Thus, when both theoptional oxynitride film and the optional film comprising titanium oxide70 are provided, the film comprising titanium oxide preferably islocated over the oxynitride film.

The film comprising titanium oxide 70 can optionally be provided overthe TC coating 107 for any embodiment of the present disclosure. Inpreferred embodiments, the film comprising titanium oxide 70 has athickness of less than 200 Å, such as from 10-75 Å, e.g., about 50 Å. Inone non-limiting example, the coating 107 and the film comprisingtitanium oxide 70 consists of the following layers (in the followingsequence moving outwardly from surface 18 of the glass pane 10′):silicon dioxide (100 Å)/ITO (1,350 Å)/Si₃N₄ (150 Å)/Si_(x)O_(y)N_(z)(900 Å)/TiO₂ (50 Å).

When provided, the film comprising titanium oxide 70 preferably isphotocatalytic, hydrophilic, or both. Suitable films of this nature aredescribed in U.S. Pat. No. 7,294,404 and Ser. No. 11/129,820 and U.S.Pat. Nos. 7,713,632 and 7,604,865 and Ser. No. 11/293,032 and U.S. Pat.Nos. 7,862,910 and 7,820,309 and 7,820,296, the salient teachings ofeach of which are incorporated herein by reference.

If desired, a non-photocatalytic film having hydrophilic properties canbe provided over the film comprising titanium oxide 70. For example, anoutermost film comprising silicon dioxide (optionally together with somealumina) can optionally be provided. In still other embodiments, thefilm comprising titanium oxide 70 is omitted, and replaced with ahydrophilic coating. For example, the film comprising titanium oxide 70in FIG. 6 can be replaced with a film comprising silicon dioxide.

Thus, certain embodiments of the invention provide a photocatalyticand/or hydrophilic coating over the transparent electrically conductivecoating 107. Particularly desirable anti-condensation properties may beobtained by providing a coated glass pane 10′ with both a lowerconductivity perimeter region 210 and a photocatalytic and/orhydrophilic coating. The lower conductivity perimeter region 210 mayremain warmer, thus decreasing the likelihood of condensation forming onthat region of the coated surface 18, while the photocatalytic and/orhydrophilic coating may cause condensation to spread into a thin sheetand thus evaporate faster.

Preferably, all the films in the coating 107 are oxide, nitride, oroxynitride films. When the coating includes one or more films of silicondioxide, silicon nitride, or silicon oxynitride, such film canoptionally be sputter deposited from one or more silicon-aluminumtargets, e.g., elemental targets comprising a sputterable materialconsisting of about 83% silicon and 17% aluminum. Thus, whenever asputtered silicon dioxide, silicon nitride, or silicon oxynitride filmis provided as part of the coating 107, the film can optionally includea small amount of aluminum. In some embodiments, all the film of thecoating 107 is sputtered film.

The transparent electrically conductive coating 107 has a number ofbeneficial properties. The discussions herein report several of theseproperties. In some cases, properties are reported for a single (e.g.,monolithic) pane 10′ bearing the TC coating 107 on one surface 18. Inother cases, these properties are reported for a double-pane IG unit 110having the TC coating 107 on the #4 surface and a triple-silverlow-emissivity coating on the #2 surface. The triple-silverlow-emissivity coating is known commercially as the LoE³-366 productfrom Cardinal CG Company. The reported properties are for a double-paneIG unit wherein both panes are clear 2.2 mm annealed soda-lime floatglass with a ½ inch between-pane space filled with an insulative gas mixof 90% argon and 10% air (“the present IG unit”). Of course, thesespecifics are by no means limiting to the invention. For example, thelow-emissivity coating can alternatively be on the #3 surface, thelow-emissivity coating can alternatively be a single or double silverlow-emissivity coating, or the low-emissivity coating can be omitted.Absent an express statement to the contrary, the discussions hereinreport determinations made using the well-known WINDOW 7.1 computerprogram (e.g., calculating center of glass data) under NFRC100-2010conditions.

At the central region 205 of the coated surface 18, the transparentelectrically conductive coating 107 can optionally have a sheetresistance of less than 30 Ω/square in combination with the coated glasspane 10′ having a monolithic visible transmittance of greater than 0.82.Preferably, the sheet resistance of the TC coating 107 at the centralregion 205 of the coated surface 18 is less than 20 Ω/square incombination with the monolithic visible transmittance of the coatedglass pane 10′ being greater than 0.86. In certain embodiments, the TCcoating 107 includes a transparent conductive oxide film 20 comprisingindium tin oxide and having a thickness of between 1,050 Å and 1,450 Å,and the sheet resistance of the coating at the central region 205 isless than 15 Ω/square in combination with the monolithic visibletransmittance of the coated glass pane 10′ being between 0.86 and 0.92.Preferably, the sheet resistance and visible transmission are within oneor more of the foregoing sets of property ranges over an entirety, or atleast a substantial entirety, of the central region 205.

The transparent electrically conductive coating 107 can providedesirable reflected color properties. For example, at the central region205, the present IG unit 110 can optionally exhibit an exteriorreflected color characterized by an “a” color coordinate of between −7and 2 (e.g., between −5 and 1, such as about −1.9) and a “b” colorcoordinate of between −9 and 0 (e.g., between −6 and −1, such as about−3.4). It will be appreciated that, in some cases, different colorproperties will be preferred for any of various reasons. The exteriorreflected color measurement is taken from the perspective of looking atthe #1 surface of the IG unit. For example, in the embodiment of FIG. 3,the exterior reflected color would be measured by directing radiationtoward the side of the IG unit 110 that faces the outdoor environment(represented schematically by the sun 7).

The reflected color properties at the perimeter region 210 preferablyare not very different from those at the central region 205. Forexample, the present pane 10′ can optionally exhibit a film-sidereflected color characterized by an “a” color coordinate that is no morethan 4 points different (in some cases, no more than 2 points different)at the perimeter region 210 than at the central region 205. In addition,the present pane 10′ can optionally exhibit a film-side reflected colorcharacterized by a “b” color coordinate that is no more than 4 pointsdifferent (in some cases, no more than 2 points different) at theperimeter region 210 than at the central region 205. This can optionallybe the case when measuring the film-side reflected color monolithically,whether the pane 10′ is from a multi-pane IG unit 110 or is intended toform a single-pane glazing. In other cases, minimizing the colordifference may be of less concern, and the difference may beconsiderably greater.

The transmitted color properties at the perimeter region 210 preferablyare not very different from those at the central region 205. Forexample, the present pane 10′ can optionally exhibit a transmitted colorcharacterized by an “a” color coordinate that is no more than 4 pointsdifferent (in some cases, no more than 2 points different) at theperimeter region 210 than at the central region 205. In addition, thepresent pane 10′ can optionally exhibit a transmitted colorcharacterized by a “b” color coordinate that is no more than 4 pointsdifferent (in some cases, no more than 2 points different) at theperimeter region 210 than at the central region 205. This may be thecase when measuring the transmitted color monolithically, whether thepane 10′ is from a multi-pane IG unit 110 or is intended to form asingle-pane glazing. However, color difference will be of less concernin some cases; thus, the difference may be greater in those cases.

The present discussion of color properties is reported using thewell-known color coordinates of “a” and “b.” In more detail, thereported color coordinates result from conventional use of thewell-known Hunter Lab Color System (Hunter methods/units, Ill. D65, 10degree observer). The present color properties can be determined asspecified in ASTM Method E 308, the relevant teachings of which areincorporated herein by reference.

In some embodiments, the coated glass pane 10′ is part of a monolithicglazing. In other embodiments, the coated substrate is part of amulti-pane insulating glazing unit 110. Reference is made to FIG. 3,which depicts a double-pane IG unit. It is to be appreciated that the IGunit 110 can alternatively have three or more panes.

Insofar as the production method is concerned, a glass pane coated witha transparent electrically conductive coating 107 is provided. Coatedglass of this nature can be purchased commercially from Cardinal CGCompany of Spring Green, Wis., USA. Alternatively, such coated glass canbe produced through a variety of well-known methods.

The production methods involve providing a glass pane 10′ having opposedfirst 18 and second 16 surfaces. The coating 107 is deposited onto asurface 18 of the glass pane 10′, e.g., as one or more discrete layers,as one or more thicknesses of graded film, or as a combination includingat least one discrete layer and at least one thickness of graded film.In some cases, the deposition method involves sputtering, e.g., DCmagnetron sputtering, which is a well-known deposition technique.Reference is made to Chapin's U.S. Pat. No. 4,166,018, the teachings ofwhich are incorporated herein by reference. If desired, the coating 107can be deposited by AC or pulsed DC sputtering from pairs of cathodes.HiPIMS and other modern sputtering methods can be used as well.

In the present production methods, a transparent conductive oxide film20 is deposited onto (optionally over one or more base films on) thefirst surface 18 of the glass pane 10′. Preferably, the transparentconductive oxide film 20, as deposited, is a sub-oxide (i.e., its oxygencontent is substoichiometric). In some cases, the deposition methodinvolves sputtering. Two non-limiting sputter deposition examples aredetailed below.

In one example, a pair of rotatable ceramic indium tin oxide targets issputtered while an uncoated glass pane is conveyed past the activatedtargets at a rate of about 36 inches per minute. The relative weightamount of the two metals is: indium 90%, tin 10%. A power of 16 kW isused, and the sputtering atmosphere is 5 mTorr with a gas flow of 900sccm argon and 10 sccm oxygen. The resulting substoichiometric indiumtin oxide film has a thickness of about 1,100 Å. Directly over thisfilm, a silicon nitride overcoat film is applied. The silicon nitride isapplied at a thickness of about 560 Å by conveying the glass pane atabout 36 inches per minute past a pair of rotary silicon aluminumtargets (83% Si, 17% Al, by weight) sputtered at a power of 31.2 kW in a5 mTorr atmosphere with a gas flow 920 sccm nitrogen.

In another example, a pair of rotatable metallic indium tin targets issputtered while an uncoated glass pane is conveyed past the activatedtargets at a rate of about 60 inches per minute. The relative weightamount of the two metals is: indium 90%, tin 10%. A power of 16 kW isused for the pair of rotary targets. The sputtering atmosphere is 5mTorr with a gas flow of 601 sccm argon and 100 sccm oxygen. Theresulting substoichiometric indium tin oxide film has a thickness ofabout 1,240 Å. Directly over this film, a silicon nitride overcoat filmis applied. The silicon nitride is applied at a thickness of about 600 Åby conveying the glass pane at about 60 inches per minute sequentiallypast a pair of rotary silicon aluminum targets (83% Si, 17% Al, byweight) sputtered at 38.6 kW in a 5 mTorr atmosphere with a gas flow 450sccm argon and 451 sccm nitrogen.

The foregoing two examples are merely exemplary. Many other sputterdeposition processes can be used to deposit the coating 107 onto thesubstrate 10′. Moreover, chemical vapor deposition, spray pyrolysis,sol-gel deposition, atomic layer deposition (ALD), or pulsed laserdeposition can alternatively be used.

Insofar as the selective heat treatment is concerned, flash treatment isused in one group of embodiments. A variety of different flash treatmentmethods can be used.

In a first method example, the entire coating 107 is flash treated in afirst step, and the perimeter region 210 is flash treated selectively(i.e., without simultaneously flash treating the central region 205) ina second step. Thus, the method can optionally involve performing afirst flash treatment on an entire area of the coated surface 107 (theentire area including both the central region 205 and the perimeterregion 210), and performing a second flash treatment that selectivelyflash treats the perimeter region, such that the perimeter region has ahigher sheet resistance than the central region. The order of these twoflash treatments is not limited. That is, the “second” flash treatmentcould be performed before the “first” flash treatment.

The second flash treatment can optionally be carried out using a maskthat covers the central region 205, and leaves the perimeter region 210exposed, during the second flash treatment. Alternatively, the secondflash treatment can involve moving a flash lamp about the perimeter ofthe coated surface 18 and operating the flash lamp to selectively treatthe perimeter region 210.

Another way to perform the second flash treatment is to use the sameflash lamp array for both the first and second steps, and to convey theglass pane 10′ past the flash lamp array in two separate passes, suchthat the first flash treatment is performed during the first pass andthe second flash treatment is performed during the second pass. Duringthe second pass, however, the lamps are selectively fired such that(during the second step) only the perimeter region 210 is flash treated.In such cases, as the glass pane 10′ moves past (e.g., beneath) the rowof lamps, all of the lamps are fired when a leading edge region (whichdefines one leg of the perimeter region 210) of the glass pane ispositioned beneath the lamps. Then, as the glass pane 10′ moves alongpast (e.g., beneath) the flash lamp array, only the edge lamps are fired(so as to only flash treat two side edge regions (which define two legsof the perimeter region 210). Finally, when a trailing edge region ofthe glass pane 10′ reaches a position aligned with (e.g., beneath) thelamps, the whole row of lamps fires.

Thus, by performing two flash treatments on the perimeter region 210, itis possible to “over-convert” the TCO at the perimeter region 210, thusyielding TCO film having a higher sheet resistance than the TCO film atthe central region 205.

The first flash treatment may be performed using a first flash bulbtreatment device 600, and the second flash treatment may be performedusing a second flash bulb treatment device 700. The first flash bulbtreatment device 600 can, for example, be a flash bulb treatment device600 arranged to flash treat an entire width of the coated surface 18.The second flash treatment can involve moving the second flash bulbtreatment device 700 about a perimeter of the coated surface 18 whileoperating the second flash bulb treatment device so as to selectivelyheat treat the perimeter region 210 of the coated surface.

FIG. 7 depicts one non-limiting arrangement of first 600 and second 700flash bulb treatment devices. Here, the two flash bulb treatment devices600, 700 are located downstream of a coater 400 on a path of substratetravel P. The coater 400 can optionally be a sputter coater having aseries of connected sputter deposition chambers through which the pathof substrate travel P extends. As shown in FIG. 7, the path of substratetravel P can be defined, for example, by a series of spaced-aparttransport rollers TR. It will be appreciated, however, that the path ofsubstrate travel P can alternatively be defined by conveyor belts,tracks along which a pallet carrying the glass pane 10′ is conveyed,etc.

In FIG. 7, the first flash bulb treatment device 600 can be configured(e.g., arranged) to remain stationary during the first flash treatment.Thus, as the coated glass pane 10′ moves along the path of substratetravel P and passes beneath the first flash bulb treatment device 600,that device can be operated so as to flash treat the entire area of thecoated surface 107. Various types of flash devices can be used. As justone example, the first flash bulb treatment device 600 can be of thenature detailed in U.S. patent application Ser. No. 14/934,706 (theteachings of this '706 application concerning the flash treatment deviceare hereby incorporated herein by reference). Equipment of this natureis commercially available from a variety of well-known commercialsuppliers, including Ncc Nano LLC of Austin, Tex., U.S.A.

The second flash bulb treatment device 700 shown in FIG. 7 includes aflash treatment head 750 that is movable relative the coated glass pane10′. This is best appreciated by referring to FIG. 8, whichschematically depicts one non-limiting type of moveable flash bulbtreatment device. Here, the flash treatment head 750 is on a gantry. Inmore detail, the flash treatment head 750 is mounted for movement alonga first support beam 740. The first support beam 740 is arrangedcross-wise to the path of the substrate travel P. The flash treatmenthead 750 is moveable along a track of the first support beam 740, suchthat the head can be moved in a direction perpendicular to the path ofsubstrate travel P. To move the flash treatment head 750 parallel to thepath of substrate travel P, the first support beam 740 can be moved(together with the flash treatment head) along two spaced-apart lateralsupport beams 720. This type of equipment is also commercially availablefrom Ncc Nano LLC, or from other well-known commercial suppliers.

In operation, the coated glass pane 10′ can optionally be moved into astationary position beneath the second flash bulb treatment device 700.The flash treatment head 750, which is spaced above the coated surface18, can then be moved so as to travel along the perimeter region 210 ofthe coated surface 18. In cases where the coated glass pane 10′ has asquare or rectangular shape, this may involve first moving the flashtreatment head 750 along a first leg of the perimeter region, thenchanging direction so as to move the head along a second leg of theperimeter region, then changing direction so as to move the head along athird leg of the perimeter region, and finally changing direction so asto move the head along a fourth leg of the perimeter region. Inembodiments of this nature, the flash treatment head 750 is constructed(e.g., arranged) such that its radiation is focused on the perimeterregion 210 of the coated surface 18, but not on the central region 205.

An alternative way to carry out the foregoing first method exampleinvolves performing the first step, not with flash treatment, butinstead using a tempering furnace or conventional oven. The first stepcan be performed, for example, by heat treating the coated glass pane10′ in a tempering furnace or conventional oven so as to convert the TCOand obtain the desired combination of high visible transmission and lowsheet resistance. The tempering furnace or oven can be operated so as toeither temper the glass or heat-strengthen it, as desired. In suchcases, the second step can be performed in the manner described above,i.e., by selectively flash treating the perimeter region 210 of thecoated surface 18. The cumulative effect of two such heat treatmentsteps on the perimeter region 210 is to “over convert” the TCO. In caseswhere the glass pane 10′ is heat strengthened, the surface stress of theglass may be, for example, from 8,000-10,000 psi.

As a second method example, the TCO at the perimeter region 210 can be“under-converted.” In such cases, the entire coating 107 can be flashtreated in a first step, and the central region 205 can be flash treatedselectively (i.e., without simultaneously flash treating the perimeterregion 210) in a second step. Here again, the order of the two flashtreatments is not limited. The “first” flash treatment could thus beperformed after the “second” flash treatment.

In this method example, the first flash treatment under-converts theentire area of the coating 107, and the second flash treatment treatsonly the central region 205. As a result, the perimeter region 210 isleft under-converted. This produces TCO film having a higher sheetresistance at the perimeter region 210 than at the central region 205.

Thus, the second method example can involve performing a first flashtreatment on an entire area of the coated surface 18 (the entire areaincluding both the central region 205 and the perimeter region 210), andperforming a second flash treatment that selectively flash treats thecentral region, such that the perimeter region has a higher sheetresistance than the central region. If desired, both flash treatmentscan be performed using the same flash bulb treatment device, which canoptionally be like the first flash bulb treatment device 600 of FIG. 7.Thus, the first flash treatment can be carried out (e.g., in the mannerdescribed above) so as to flash treat the entire area of the coatedsurface 18. In connection with the second flash treatment, one option isto provide a mask that covers the perimeter region 210 of the coatedsurface 18 during the second flash treatment. Another option is toperform the second flash treatment by using the same flash lamp arrayfor both the first and second steps, but to selectively fire the lampsduring the second step such that only the central region 205 is flashtreated, whereas during the first step, the entire area of the coatedsurface 18 is flash treated.

In still other examples, the method may involve flash treating only thecentral region 205 of the coated surface without ever flash treating theperimeter region 210. In such cases, the TC coating 107 can be deposited(or otherwise provided) in a form having a lower level of electricalconductivity, which is desired for the perimeter region 210 of thecoated surface 18. The central region 205 of the coated surface 18 canthen be flash treated selectively to convert that region of the TCcoating 107 so as to have a higher level of electrical conductivity thanthe perimeter region 210. Such selective flash treatment of the centralregion 205 can be carried out, for example, using a mask as describedabove.

Thus, in one group of embodiments, the TC coating 107 is a flash-treatedcoating. In certain embodiments of this nature, the TC coating 107 (orat least one region thereof) is subjected to an ultra-high-power (“UHP”)flash-treatment that involves a peak pulse power of 15 kW/cm² orgreater, e.g., in the range of 15-45 kW/cm², or even 20 kW/cm² orgreater, e.g., in the range of 20-45 kW/cm². The terms “ultra-high-powerflash treatment” and “UHP flash treatment” are defined for purposes ofthe present disclosure to mean flash treatment at a peak pulse power of15 kW/cm² or greater. It will be appreciated that this is higher thanthe peak pulse powers commonly reported for conventional flash lamptreatment. Thus, the TC coating 107 may comprise a flash-treatedtransparent conductive oxide film having a morphology characterized byUHP flash-treatment at 15-45 kW/cm². Due to the rapid temperature changeof the film, a distinctive average stress condition may result.

In another group of embodiments, the selective heat treatment involvesperforming a laser treatment on the coated surface 18. The lasertreatment can involve, for example, treating the entire area of thecoated surface 18 in a first step of the method, and selectivelytreating the perimeter region 210 in a second step of the method. Thefirst treatment can convert a transparent conductive oxide film 20 ofthe coating 107 at the central region 205 to a desired (e.g., optimal)level of electrical conductivity, and the second treatment can“over-convert” the TCO film 20 at the perimeter region 210. Theperimeter region 210 can thus be made less electrically conductive thanthe central region 205.

The first laser treatment step can, for example, involve moving thecoated glass pane 10′ beneath a stationary laser treatment device. Asthe glass pane 10′ moves past this device, it can be operated so as toheat treat the entire area of the coating 107. If desired, the equipmentused can be similar to that shown in FIG. 7, except that the first flashbulb treatment device 600 is replaced with a first laser treatmentdevice and the second flash bulb treatment device 700 is replaced with asecond laser treatment device. Equipment of this nature is commerciallyavailable from a variety of well-known commercial suppliers, includingManz AG of Reutlingen, Germany. Thus, the second laser treatment devicecan optionally be movable about the perimeter of the coated glass pane10′ in the same manner (e.g., using a gantry) as the flash treatmenthead 750 of FIG. 7. In such cases, the second laser treatment device canbe moved and operated so as to focus its radiation selectively on theperimeter region 210 of the coated surface 18.

An alternative way to carry out the foregoing method example involvesperforming the first heat treatment step, not with a laser, but insteadusing a tempering furnace or conventional oven. The first step can beperformed, for example, by heat treating the coated glass pane 10′ in atempering furnace or conventional oven so as to convert the TCO andobtain the desired combination of high visible transmission and lowsheet resistance. The tempering furnace or oven can be operated so as toeither temper the glass or heat-strengthen it, as desired. In suchcases, the second step can be performed in the manner described above,i.e., by selectively laser treating the perimeter region 210 of thecoated surface 18. The cumulative effect of two such heat treatmentsteps on the perimeter region 210 is to “over convert” the TCO. In caseswhere the glass pane 10′ is heat strengthened, the surface stress of theglass may be, for example, from 8,000-10,000 psi.

Another possibility is to perform a first laser treatment on the entirearea of the coated surface 18 in a first step of the method, and toselectively laser treat the central region 205 in a second step of themethod. The two laser treatments performed on the central region 205 canconvert that region of the TCO film 20 to a desired (e.g., optimal)combination of electrical conductivity and visible transmission, whilethe single laser treatment performed on the perimeter region 210 canleave that region of the coating “under converted,” and thus lesselectrically conductive than the central region 205.

Still another possibility is to laser treat only the central region 205of the coated surface 18 without ever laser treating the perimeterregion 210. In such cases, the TC coating 107 can be deposited (orotherwise provided) so as to have a lower level of electricalconductivity, which is desired for the perimeter region 210 of thecoated surface 18. The central region 205 of the coated surface 18 canthen be laser treated selectively to convert that region of the TCcoating 107 so as to have a higher level of electrical conductivity thanthe perimeter region 210. If desired, a laser head can be mounted on thecrosswise support beam 740 of a gantry like that shown in FIG. 8, andthe laser head moved over the central region 205 of the coated surface18 while the laser emission is focused so as to selectively treat onlythe central region of the coated surface. Another possibility is toprovide a mask over the perimeter region 210 of the coated surface 18,while operating the laser head, such that only the central region 205 islaser treated.

Yet another possibility is to laser treat the entire coated surface 18,and to selectively flash treat either the central region 205 or theperimeter region 210 of the coated surface, such that the transparentelectrically conductive coating 107 has a higher electrical conductivityat the central region than it does at the perimeter region.

A further possibility is to flash treat the entire coated surface 18,and to selectively laser treat either the central region 205 or theperimeter region 210 of the coated surface, such that the transparentelectrically conductive coating 107 has a higher electrical conductivityat the central region than it does at the perimeter region.

In embodiments involving a laser treatment step, the laser radiation canoptionally have a wavelength between 500 and 2,000 nm, such as between520 nm and 1,300 nm. Laser radiation of this nature may be well absorbedby the TC coating 107 while being only very weakly absorbed by the glasspane 10′. Laser diodes emitting at a wavelength of about 808 nm, 880 nm,940 nm, or 980 nm can optionally be used.

In certain embodiments, the laser treatment step uses excimer lasers,which have shorter wavelengths. In such cases, the laser radiation mayhave a wavelength between 100 and 400 nm, and typically between 125 nmand 355 nm, such as 126 nm (Ar2), 146 nm (Kr2), 157 (F2), 172 nm or 175nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 248 nm (KrF), 282 nm (XeBr), 308nm (XeCl), or 351 nm (XeF). While glass is more absorbent of theseshorter wavelengths, the coating 107 will tend to absorb suchwavelengths so strongly that little radiation reaches the glass.

Thus, various embodiments of the invention provide a heat treatmentmethod that includes two heat treatment steps. In some cases, the firstheat treatment step involves tempering the coated glass pane 10′. Insuch cases, the tempering typically involves heating the glass pane 10′to a temperature of at least 680° C. For example, the glass may beplaced in a furnace maintained at about 680-705° C. (preferablycontrolled to 690-700° C.). The glass is typically held in the furnacefor 100-120 seconds with constant movement to improve temperatureuniformity. This is intended to raise the glass temperature to about640° C. The glass is then removed from the furnace and subjected to astream of air for about 50 seconds such that the glass is cool enoughfor an operator to handle.

In cases where tempering is used for the first heat treatment step, thesecond heat treatment step involves selectively heat treating either thecentral region 205 or the perimeter region 210 of the coated surface 18,such that the transparent electrically conductive coating 107 has ahigher electrical conductivity at the central region than it does at theperimeter region. The second heat treatment can involve, for example,selectively flash treating or selectively laser treating either thecentral region 205 or the perimeter region 210 of the coated surface 18.Flame treatment may alternatively be used. Another alternative is toreplace the flash bulb or laser treatment system with another type ofdevice that focuses infrared radiation onto the coated surface 18. Thismay involve using mirrors or lenses to obtain the desired power per unitarea.

Preferably, the selective heat treatment technique is one that allowsthe rear surface 16 of the glass pane 10′ to remain at a temperature of150 degrees C. or less during the selective heat treatment. In someembodiments, the tempering involves heating the glass pane 10′ to atemperature of at least 680° C., and the second heat treatment involvesselectively flash or laser treating the perimeter region 210 of thecoated surface 18, such that the rear surface 16 of the glass pane 10′is maintained at a temperature of 150 degrees C. or less during thesecond heat treatment.

Thus, in certain embodiments, the first heat treatment involvestempering the coated glass pane 10′ such that, following the tempering,the glass pane is tempered glass having a surface stress of greater than10,000 psi. In such cases, following the second heat treatment, theglass pane 10′ preferably remains tempered glass having the surfacestress of greater than 10,000 psi, such as greater than 10,000 psi andless than 15,000 psi, or perhaps optimally 12,000 psi to 15,000 psi.

Thus, the invention provides a glass pane 10′ having a transparentelectrically conductive coating 107 on a surface 18 of the glass pane,such that the glass pane has a coated surface. The coated surface 18 hasa central region 205 and a perimeter region 210. The transparentelectrically conductive coating 107 has a higher electrical conductivityat the central region 205 than it does at the perimeter region 210. Thesheet resistance of the coating 107 is higher at the perimeter region210 than it is at the central region 205. Yet the coating 107 has avisible transmission that is substantially the same at the perimeterregion 210 as it is at the central region 205. The thickness of thecoating 107 is also preferably the same, or at least substantially thesame, at the perimeter region 210 as it is at the central region 205.

FIG. 2 depicts an embodiment wherein the glass pane 10′ is mounted to aframe 300. Thus, the illustrated glazing 500 includes both the coatedglass pane 10′ and the frame 300. The perimeter region 210 of the coatedsurface 18 is adjacent to the frame 300, while the central region 205 ofthe coated surface is spaced inwardly from the frame. The frame 300 canbe any conventional window, door, or skylight frame. In the embodimentof FIG. 2, the pane 10′ can optionally be part of a multiple-paneinsulating glazing unit. Alternatively, the pane 10′ in FIG. 2 can bemonolithic.

FIG. 3 depicts an embodiment wherein a glazing includes a frame 200 anda multiple-pane insulating glass unit 110. The IG unit 110 is mounted tothe frame 300. The IG unit 110 includes an inboard glass pane 10′ and anoutboard glass pane 10. The IG unit 110 has at least one between-panespace 800. The outboard glass pane 10 defines an external surface 12that is exposed to an outdoor environment (as represented by the sun 7).Thus, the external surface 12 of the outboard glass pane 10 is inperiodic contact with rain. The inboard glass pane 10′ defines anexternal surface 18 that is exposed to a room-side environment inside abuilding. In the embodiment of FIG. 3, the external surface 18 of theinboard glass pane 10′ has a transparent electrically conductive coating107, so as to define a coated surface. This coated surface 18 has acentral region 205 and a perimeter region 210. The transparentelectrically conductive coating 107 has a higher electrical conductivityat the central region 205 than it does at the perimeter region 210. Yetthe coating 107 has a visible transmission that is substantially thesame at the perimeter region 210 as it is at the central region 205. Thethickness of the coating 107 is also preferably the same, or at leastsubstantially the same, at the perimeter region 210 as it is at thecentral region 205.

In embodiments involving an insulating glass unit, one or more internalsurfaces (e.g., 14, 16) can optionally have a low-emissivity coating.For example, the #2 surface 14 of the IG unit 110 of FIG. 3 canoptionally have a low-emissivity coating. Additional or alternatively, alow-emissivity coating can optionally be provided on the #3 surface.When provided on any internal surface of an IG unit, the low-emissivitycoating preferably includes at least one silver-inclusive film, whichmay contain more than 50% silver by weight (e.g., a metallic silverfilm). In some embodiments, the low-emissivity coating includes three ormore infrared-reflective films (e.g., silver-containing films).Low-emissivity coatings with three or more infrared-reflective films aredescribed in U.S. patent application Ser. No. 11/546,152 and U.S. Pat.Nos. 7,572,511 and 7,572,510 and 7,572,509 and Ser. No. 11/545,211 andU.S. Pat. Nos. 7,342,716 and 7,339,728, the salient teachings of each ofwhich are incorporated herein by reference. In other cases, thelow-emissivity coating can be a “single silver” or “double silver”low-emissivity coating, which are well known to skilled artisans.

While some preferred embodiments of the invention have been described,it should be understood that various changes, adaptations andmodifications may be made therein without departing from the spirit ofthe invention and the scope of the appended claims.

1. A glass pane having a transparent electrically conductive coating ona surface of the glass pane, such that the glass pane has a coatedsurface, the coated surface having a central region and a perimeterregion, the transparent electrically conductive coating having a higherelectrical conductivity at the central region than it does at theperimeter region.
 2. The glass pane of claim 1 wherein the transparentelectrically conductive coating comprises a transparent electricallyconductive oxide film that is oxidized to a different extent at thecentral region than it is at the perimeter region.
 3. The glass pane ofclaim 1 wherein the transparent electrically conductive coatingcomprises an indium tin oxide layer that is oxidized to a differentextent at the central region than it is at the perimeter region.
 4. Theglass pane of claim 1 wherein the transparent electrically conductivecoating has a sheet resistance that is at least 5 Ω/square higher at theperimeter region than it is at the central region.
 5. The glass pane ofclaim 1 wherein the transparent electrically conductive coating has avisible transmission that is substantially the same at the perimeterregion as it is at the central region.
 6. The glass pane of claim 5wherein the visible transmission at the perimeter region is no more than2% different from the visible transmission at the central region.
 7. Theglass pane of claim 1 wherein the transparent electrically conductivecoating has a thickness of less than 3,000 Å, the thickness of thetransparent electrically conductive coating being substantially the sameat the perimeter region as it is at the central region.
 8. The glasspane of claim 1 wherein the transparent electrically conductive coatingcomprises an indium tin oxide film having a thickness of less than 1,800Å.
 9. The glass pane of claim 1 wherein the glass pane is annealed glasshaving a surface stress of less than 3,500 psi.
 10. The glass pane ofclaim 1 wherein, at the central region, the transparent electricallyconductive coating has a sheet resistance of less than 30 Ω/square incombination with the coated glass pane having a monolithic visibletransmittance of greater than 0.82.
 11. The glass pane of claim 10wherein, at the central region, the sheet resistance of the transparentelectrically conductive coating is less than 20 Ω/square in combinationwith the monolithic visible transmittance of the coated glass pane beinggreater than 0.86.
 12. The glass pane of claim 11 wherein thetransparent electrically conductive coating comprises an indium tinoxide film having a thickness of between 1,050 Å and 1,450 Å, and at thecentral region the sheet resistance of the transparent electricallyconductive coating is less than 15 Ω/square in combination with themonolithic visible transmittance of the coated glass pane being between0.86 and 0.92.
 13. The glass pane of claim 1 wherein the perimeterregion of the coated surface has a width that is greater than ⅛ inch butless than 8 inches.
 14. The glass pane of claim 1 wherein the glass paneis mounted in a frame, the perimeter region of the coated surface beingadjacent to the frame and surrounding the central region of the coatedsurface.
 15. The glass pane of claim 1 wherein the glass pane is part ofa multiple-pane insulating glass unit that comprises at least two glasspanes and has at least one between-pane space, the multiple paneinsulating glass unit having two external surfaces and a plurality ofinternal surfaces, each of the internal surfaces being exposed to abetween-pane space of the multiple-pane insulating glass unit, each ofthe two external surfaces being exposed to an environment external tothe multiple-pane insulating glass unit, the transparent electricallyconductive coating being on one of the two external surfaces of themultiple-pane insulating glass unit.
 16. The glass pane of claim 1wherein the multiple-pane insulating glass unit is mounted to a windowframe of a building, the window frame retaining the multiple-paneinsulating glass unit in a vertical orientation such that the coatedsurface is exposed to a room-side environment inside the building.
 17. Amultiple-pane insulating glass unit comprising at least two glass panesand having at least one between-pane space, the multiple pane insulatingglass unit having two external surfaces and a plurality of internalsurfaces, each of the internal surfaces being exposed to a between-panespace of the multiple-pane insulating glass unit, each of the twoexternal surfaces being exposed to an environment external to themultiple-pane insulating glass unit, a desired one of the two externalsurfaces having a transparent electrically conductive coating so as todefine a coated surface, the coated surface having a central region anda perimeter region, the transparent electrically conductive coatinghaving a higher electrical conductivity at the central region than itdoes at the perimeter region.
 18. The multiple-pane insulating glassunit of claim 17 wherein the transparent electrically conductive coatinghas a visible transmission that is substantially the same at theperimeter region as it is at the central region.
 19. A glazingcomprising a frame and a multiple-pane insulating glass unit, themultiple-pane insulating glass unit being mounted to the frame, themultiple-pane insulating glass unit comprising an inboard glass pane andan outboard glass pane and having at least one between-pane space, theoutboard glass pane defining an external surface that is exposed toperiodic contact with rain, the inboard glass pane defining an externalsurface that is exposed to a room-side environment inside a building,the external surface of the inboard glass pane having a transparentelectrically conductive coating so as to define a coated surface, thecoated surface having a central region and a perimeter region, thetransparent electrically conductive coating having a higher electricalconductivity at the central region than it does at the perimeter region.20. The glazing of claim 19 wherein the transparent electricallyconductive coating has a visible transmission that is substantially thesame at the perimeter region as it is at the central region.
 21. Theglazing of claim 19 wherein the glazing is a window, the frame is awindow frame, and the window frame retains the multiple-pane insulatingglass unit in a vertical orientation.
 22. A glass pane having atransparent electrically conductive coating on a surface of the glasspane, such that the glass pane has a coated surface, wherein the glasspane is tempered glass having a surface stress of greater than 10,000psi, the coated surface having a central region and a perimeter region,the transparent electrically conductive coating having a higherelectrical conductivity at the central region than it does at theperimeter region.
 23. The glass pane of claim 22 wherein the surfacestress of the tempered glass is between 12,000 psi and 15,000 psi. 24.The glass pane of claim 22 wherein the transparent electricallyconductive coating comprises a transparent electrically conductive oxidefilm that is oxidized to a different extent at the central region thanit is at the perimeter region.
 25. The glass pane of claim 22 whereinthe transparent electrically conductive coating has a sheet resistancethat is at least 5 Ω/square higher at the perimeter region than it is atthe central region.
 26. The glass pane of claim 22 wherein thetransparent electrically conductive coating has a visible transmissionthat is substantially the same at the perimeter region as it is at thecentral region.
 27. The glass pane of claim 26 wherein the visibletransmission at the perimeter region is no more than 2% different fromthe visible transmission at the central region.
 28. The glass pane ofclaim 22 wherein the transparent electrically conductive coating has athickness of less than 3,000 Å, and wherein at the central region thetransparent electrically conductive coating has a sheet resistance ofless than 30 Ω/square in combination with the coated glass pane having amonolithic visible transmittance of greater than 0.82.